[0004] 上述降低催化裂化NOx排放组合物都可以有效地降低催化裂化烟气中的NOx排放， 但也存在NOx脱除率相对较低、组合物中含有对催化裂化主催化剂有副作用的元素如IA或IB和或ΠΒ元素Cu、Ag，这类元素在催化裂化反应过程中，会导致催化裂化主催化剂活性降低、气体产品中氢气产率增加等问题。 [0004] The above-described compositions to reduce NOx emissions cracking can effectively reduce NOx emissions in FCC flue gas, but there is a relatively low NOx removal rate, contained in the composition has an adverse effect on the main FCC catalyst elements such as IA or IB and ΠΒ or elements Cu, Ag, such elements in a catalytic cracking reaction, leads to the main catalyst cracking activity decreases, problems such as an increase in product gas hydrogen yields.

发明内容 SUMMARY

[0005] 本发明的目的是提供一种用于降低催化裂化再生烟气NOx排放并具有CO助燃功能的组合物及其制备方法，这种组合物的NOx脱除率更高、不含对FCC主催化剂产生负作用的成分。 [0005] The object of the present invention is to provide a composition and method for preparing FCC regenerator flue gas having CO NOx emissions and combustion function is reduced, a higher NOx removal rate of such a composition, free of FCC a main catalyst component of a negative effect.

[0006] 为了解决上述技术问题，本发明采用的技术方案是：一种用于降低催化裂化再生烟气NOx排放并具有CO助燃功能的组合物，含有以组合物重量计的以下成分： [0006] To solve the above technical problem, the technical solution adopted by the invention is: a method for reducing NOx emissions from FCC regenerator flue gas and having a CO combustion functional composition comprising the following ingredients in the weight of the composition:

[0023] (2)称取除镧之外的镧系元素的硝酸盐或氯化物放入反应釜中，加入蒸馏水，使溶液的体积能够进行等体积浸渍;在搅拌情况下，慢慢加入到步骤(1)的反应釜中，静置18-24 小时； [0023] (2) Weigh lanthanide nitrate or chloride of lanthanum addition into a reaction kettle, distilled water was added to bring the volume of the solution can be incipient wetness impregnation; in with stirring, was slowly added to the the reaction vessel of step (1) was allowed to stand for 18-24 hours;

[0025] (4)用贵金属水溶液浸渍步骤(3)得到的组合物，静置8-12小时，将上述浸渍物在烘箱中120-140°C烘烤2-4小时，然后在马弗炉中550-650 °C下焙烧4-6小时，得到目的组合物。 [0025] (4) obtained in the step of impregnating an aqueous solution of noble metal (3) composition was allowed to stand 8-12 h, the impregnation baked in an oven at 120-140 ° C for 2-4 hours and then in a muffle furnace calcined in 4-6 hours 550-650 ° C, to give the desired composition.

[0026]本发明的有益效果是:组合物的NOx脱除率更高;组合物中不含等对催化裂化主催化剂有害的成分;双贵金属使组合物的NOx脱除性能更加稳定，寿命更长。 [0026] Advantageous effects of the present invention are: a higher NOx removal rate of the composition; and the like of the composition does not contain ingredients harmful to the main catalyst cracking; noble metal double the NOx removal performance of the composition is more stable, more life long.

具体实施方式 detailed description

[0027]下面结合具体实施方式对本发明作进一步详细说明： [0027] DETAILED DESCRIPTION The following embodiments of the present invention will be further described in detail:

[0030] 本发明提供一种降低催化裂化烟气NOx排放，并同时具有CO助燃功能的组合物的制备是由以下方法但不仅限于以下方法制备。 Preparation [0030] The present invention provides a method of reducing NOx emissions from FCC flue gas, and also has the function of CO combustion compositions are prepared by the following method, but the method is not limited.⑴称取适量的统式为LaAl xZnyMnzO3的钙钛矿组分、三元水滑石组分和拟薄水铝石放入烧杯中；（2)将三种组分机械混合均匀；（3)称取适量除镧之外的镧系元素，如铈、镨、钕的硝酸盐或氯化物放入另一个烧杯中，加入适量的蒸馏水，是溶液的体积能够进行等体积浸渍；（4)将除镧之外的镧系元素，如铈、镨、钕的硝酸盐或氯化物溶液在搅拌情况下，慢慢加入盛有适量的统式为LaAl xZnyMnzO3的钙钛矿组分和三元水滑石组分的烧杯中，静置18-24小时。 ⑴ weighed amount of component a perovskite-type system LaAl xZnyMnzO3, the hydrotalcite component and a quasi boehmite into a beaker; (2) the three components are mechanically mixed uniformly; (3), said take appropriate lanthanide elements other than lanthanum, such as cerium, praseodymium, neodymium nitrate or chloride into a separate beaker, adding an appropriate amount of distilled water, the volume of the solution can be incipient wetness impregnation; (4) in addition to the lanthanide other than La, such as cerium, praseodymium, neodymium nitrate or chloride solution with stirring, was added slowly filled with an appropriate amount of a perovskite type system components LaAl xZnyMnzO3 group and hydrotalcite min in a beaker, allowed to stand for 18-24 hours.（5)将上述浸渍物在烘箱中120-140°C烘烤2-4小时，然后在马弗炉中550-650 °C下焙烧4-6小时。 (5) The above impregnation 120-140 ° C baked in an oven for 2-4 hours, and then calcined in a muffle furnace at 550-650 ° C 4-6 hours.（6)用适量的贵金属水溶液浸渍步骤(5) 得到的组合物，静置8-12小时，将上述浸渍物在烘箱中120-140 °C烘烤2-4小时，然后在马弗炉中550-650°C下焙烧6小时，得到本发明的目的组合物。 (6) obtained in the step of impregnating an aqueous solution with a suitable amount of a noble metal (5) composition was allowed to stand 8-12 h, the impregnation baked in an oven at 120-140 ° C for 2-4 hours and then in a muffle furnace calcined for 6 hours 550-650 ° C, to obtain the composition object of the present invention.

[0031] 以下将通过具体实施例对本发明作进一步的阐述，所有的实施例完全按照本发明所述的步骤进行操作。 [0031] Here it will be further illustrated by way of specific embodiments of the present invention, embodiments, examples and embodiments, all the steps in the present invention.

[0032] 实施例1 [0032] Example 1

[0033] 称取通式为LaAlo.AZntL1Mno.5〇3的钙钛矿52.0g(干基为100wt%)放入容积为500ml 的烧杯中1，再称取58.88铁镁铝三元水滑石（干基为68#%)和258拟薄水铝石（干基为68wt%)放入烧杯1中，并将它们搅拌均匀;称取27.7g硝酸镨(氧化物含量45wt%)放入容积为IOOrnl的烧杯2中，加入68g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置20小时;将其在烘箱中120°C烘烤3小时，然后在马弗炉中580 °C下焙烧6小时。 [0033] Weigh the general formula of a perovskite LaAlo.AZntL1Mno.5〇3 52.0g (dry basis of 100wt%) into a beaker of 500ml volume of 1, then weighed 58.88 iron magnesium aluminum hydrotalcite ( # 68% dry basis) 258 pseudoboehmite and boehmite (68 wt% dry basis) put in a beaker, and uniformly stirred; Weigh 27.7g praseodymium nitrate (45 wt% oxide content) is placed in a volume 2 IOOrnl beaker, 68g of distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 20 hours; it in an oven bake 120 ° C for 3 hours and then calcined in a muffle furnace at 580 ° C 6 hours.

[0034] 取50g上述制得组合物放入烧杯3中，取5. OgPd含量为3000yg/g的水溶液和2.5gRh 含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入17.5g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置10小时，将上述浸渍物在烘箱中130 °C烘烤3小时，然后在马弗炉中600 °C下焙烧5小时，得到本发明的目的组合物1〇 [0034] Take 50g above-prepared composition was placed in a beaker 3, take the amount of aqueous solution 5. OgPd 3000yg / g and a content 2.5gRh 4000yg / g was placed in beaker 4, again in a beaker was added 17.5g 4 stir distilled water, stirring the beaker 4 in the case where the solution was slowly added to the beaker 3, complete addition stirring was continued for 30 minutes and allowed to stand for 10 hours, the above-described impregnation baked in an oven at 130 ° C for 3 hours, and then the horse calcined in muffle furnace for 5 hours 600 ° C, to obtain the composition object of the present invention 1〇

[0035] 实施例2 [0035] Example 2

[0036] 称取通式为LaAlo.5Zno.4Mno.iO3的钙钛矿42.0g(干基为100wt%)放入容积为500ml 的烧杯中1，再称取70.6g锌镁铝三元水滑石（干基为68wt%)和20g拟薄水铝石（干基为68wt% )放入烧杯1中，并将它们搅拌均匀;称取37.2g硝酸铈(氧化物含量45wt % )放入容积为100mL的烧杯2中，加入66g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置24小时;将其在烘箱中140°C烘烤2小时，然后在马弗炉中620°C下焙烧7小时。 [0036] Weigh the formula LaAlo.5Zno.4Mno.iO3 perovskite 42.0 g (on dry basis of 100wt%) into a beaker of 500ml volume of 1, then weighed 70.6g magnesium aluminum hydrotalcite (dry basis 68wt%) and 20g quasi boehmite (on dry basis of 68wt%) into a beaker, and uniformly stirred; Weigh 37.2g of cerium nitrate (oxide content 45wt%) into the volume 100mL beaker 2, 66g of distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 24 hours; it in an oven bake 140 ° C for 2 hours and then calcined in a muffle furnace at 620 ° C 7 hours.

[0037] 取50g上述制得组合物放入烧杯3中，取10.(^?(1含量为300(^8/^的水溶液和1.25gRh含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入12.5g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置12小时，将上述浸渍物在烘箱中130 °C烘烤4小时，然后在马弗炉中640 °C下焙烧4小时，得到本发明的目的组合物2。 Aqueous [0037] Take 50g above-prepared composition was placed in a beaker 3, taken 10. (^? (1 content 300 (8 ^ / ^ and aqueous 1.25gRh content 4000yg / g was placed in beaker 4, the then the beaker was added 12.5g of distilled water stir 4, 4 with stirring in the beaker was slowly added to the beaker 3, complete addition stirring was continued for 30 minutes and allowed to stand for 12 hours, the above was immersed in a 130 ° C drying oven baked 4 hours and then calcined for 4 hours in a muffle furnace at 640 ° C, to afford the desired composition 2 of the present invention.

[0038] 实施例3 [0038] Example 3

[0039] 称取通式为LaAlo.5Zno.4Mno.iO3的钙钛矿35.0g(干基为100wt%)放入容积为500ml 的烧杯中1，再称取80.9g锰镁铝三元水滑石（干基为68wt%)和30g拟薄水铝石（干基为68wt% )放入烧杯1中，并将它们搅拌均匀;称取32.2g硝酸铈(氧化物含量45wt % )放入容积为100mL的烧杯2中，加入73g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置23小时;将其在烘箱中120°C烘烤4小时，然后在马弗炉中650 °C下焙烧6小时。 [0039] Weigh the formula LaAlo.5Zno.4Mno.iO3 perovskite 35.0 g (on dry basis of 100wt%) into a beaker of 500ml volume of 1, then weighed 80.9g Mn Mg-Al hydrotalcite (dry basis 68wt%), and 30g of boehmite and pseudoboehmite (dry basis 68wt%) into a beaker, and uniformly stirred; Weigh 32.2g of cerium nitrate (oxide content 45wt%) into the volume 100mL beaker 2, 73g of distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 23 hours; it in an oven bake 120 ° C for 4 hours and then calcined in a muffle furnace at 650 ° C 6 hours.

[0040] 取50g上述制得组合物放入烧杯3中，取3.3gPd含量为3000yg/g的水溶液和2.5gRh 含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入19.2g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置8小时，将上述浸渍物在烘箱中120 °C烘烤5小时，然后在马弗炉中610 °C下焙烧6小时，得到本发明的目的组合物3〇 [0040] Take 50g above-prepared composition was placed in a beaker 3, an amount of an aqueous solution taken 3.3gPd 3000yg / g and a content 2.5gRh 4000yg / g was placed in beaker 4, 19.2g distilled water and then added to the beaker 4 stir the mixture was stirred 4 in the case where the beaker was slowly added in 3 beaker, stirred solution was added after a further 30 minutes, allowed to stand for 8 hours, the above-described impregnation baked in an oven at 120 ° C for 5 hours and then in a muffle calcined for 6 hours oven 610 ° C, to obtain the composition object of the present invention 3〇

[0041 ] 实施例4 [0041] Example 4

[0042] 称取通式为LaAlo.7Zn〇.^ntL1O3的钙钛矿65.0g(干基为100wt%)放入容积为500ml 的烧杯中1，再称取41.2g锌镁铝三元水滑石（干基为68wt% )和20g拟薄水铝石（干基为68wt%)放入烧杯1中，并将它们搅拌均匀;称取28.7g硝酸钕(氧化物含量45wt%)放入容积为IOOrnl的烧杯2中，加入63g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置24小时;将其在烘箱中140°C烘烤2小时，然后在马弗炉中580 °C下焙烧6小时。 [0042] was weighed into LaAlo.7Zn〇 formula. ^ NtL1O3 perovskite 65.0 g of (dry basis of 100wt%) in a volume of 500ml beaker 1, and then weighed 41.2g magnesium aluminum hydrotalcite (dry basis 68wt%) and 20g quasi boehmite (on dry basis of 68wt%) into a beaker, and uniformly stirred; Weigh 28.7g of neodymium nitrate (oxide content of 45wt%) into the volume 2 IOOrnl beaker, 63g of distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 24 hours; it in an oven bake 140 ° C for 2 hours and then calcined in a muffle furnace at 580 ° C 6 hours.

[0043] 取50g上述制得组合物放入烧杯3中，取2.5gPd含量为3000yg/g的水溶液和5.6gRh 含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入16.9g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置11小时，将上述浸渍物在烘箱中120 °C烘烤6小时，然后在马弗炉中560 °C下焙烧6小时，得到本发明的目的组合物4〇 [0043] Take 50g above-prepared composition was placed in a beaker 3, an amount of an aqueous solution taken 2.5gPd 3000yg / g and a content 5.6gRh 4000yg / g was placed in beaker 4, 16.9g distilled water and then added to the beaker 4 stir the mixture was stirred 4 in the case where the beaker was slowly added in 3 beaker, stirred solution was added after a further 30 minutes, allowed to stand for 11 hours to impregnate the above-described baking in an oven at 120 ° C for 6 hours, and then in a muffle calcined for 6 hours oven 560 ° C, to obtain the composition object of the present invention 4〇

[0044] 实施例5 [0044] Example 5

[0045] 称取通式为LaAlo.sZno.SMntL1O3的钙钛矿15.0g(干基为lOOwt%)放入容积为500ml 的烧杯中1，再称取80.4锰镁铝三元水滑石（干基为68#%)和258拟薄水铝石（干基为68wt% )放入烧杯1中，并将它们搅拌均匀;称取30.7g硝酸铈(氧化物含量45wt % )放入容积为100mL的烧杯2中，加入62.5g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置18小时;将其在烘箱中130°C烘烤3小时，然后在马弗炉中640 °C下焙烧5小时。 [0045] formula LaAlo.sZno.SMntL1O3 weighed 15.0 g of the perovskites (dry basis lOOwt%) into a beaker of 500ml volume of 1, then weighed 80.4 Mn Mg-Al hydrotalcite (dry basis # 68%) and 258 quasi boehmite (68 wt% dry basis) put in a beaker, and uniformly stirred; Weigh 30.7g of cerium nitrate (45 wt% oxide content) is placed in a volume of 100mL in beaker 2, 62.5g distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 18 hours; it in an oven 130 baking ° C for 3 hours and then calcined in a muffle furnace at 640 ° C 5 hours.

[0046] 取50g上述制得组合物放入烧杯3中，取1.7gPd含量为3000yg/g的水溶液和2.5gRh 含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入20.8g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置9小时，将上述浸渍物在烘箱中120 °C烘烤5小时，然后在马弗炉中550 °C下焙烧6小时，得到本发明的目的组合物5〇 [0046] Take 50g above-prepared composition was placed in a beaker 3, an amount of an aqueous solution taken 1.7gPd 3000yg / g and a content 2.5gRh 4000yg / g was placed in beaker 4, 4 in a beaker and then added 20.8g of distilled water stir the mixture was stirred 4 in the case where the beaker was slowly added in 3 beaker, stirred solution was added after a further 30 minutes, allowed to stand for 9 hours, the above was immersed in an oven at 120 ° C bake for 5 hours and then in a muffle calcined for 6 hours oven 550 ° C, to obtain the composition object of the present invention 5〇

[0047] 实施例6 [0047] Example 6

[0048] 称取通式为LaAltL3Zno.SMntL1O3的钙钛矿45.0g(干基为100wt%)放入容积为500ml 的烧杯中1，再称取32.2g锌镁铝三元水滑石（干基为68wt% )和23g拟薄水铝石（干基为68wt% )放入烧杯1中，并将它们搅拌均匀；称取25.3g硝酸镨(氧化物含量45wt% )放入容积为100mL的烧杯2中，加入48g蒸馏水，搅拌使其完全溶解;然后在搅拌情况下，将烧杯2中溶液缓慢加入烧杯1中，加完后搅拌30分钟，静置22小时;将其在烘箱中140°C烘烤3小时，然后在马弗炉中650 °C下焙烧4小时。 [0048] Weigh the general formula of a perovskite LaAltL3Zno.SMntL1O3 45.0 g (on dry basis of 100wt%) into a beaker of 500ml volume of 1, then weighed 32.2g magnesium aluminum hydrotalcite (dry basis 68wt%) and 23g quasi boehmite (on dry basis of 68wt%) into a beaker, and uniformly stirred; beaker Weigh 25.3g praseodymium nitrate (oxide content of 45wt%) into a volume of 100mL 2 in 48g of distilled water was added, stirred and completely dissolved; then, in the case of stirring, the beaker was slowly added in 2 1 beaker, was added after stirring for 30 minutes and allowed to stand for 22 hours; it is baked in an oven at 140 ° C in bake for 3 hours and then calcined in a muffle furnace at 650 ° C 4 hours.

[0049] 取50g上述制得组合物放入烧杯3中，取1.7gPd含量为3000yg/g的水溶液和0.6gRh 含量4000yg/g的水溶液放入烧杯4中，在再烧杯4中加入22.7g蒸馏水搅拌均匀，搅拌情况下将烧杯4中溶液缓慢加入烧杯3中，溶液加完后继续搅拌30分钟，静置10小时，将上述浸渍物在烘箱中120 °C烘烤6小时，然后在马弗炉中620 °C下焙烧5小时，得到本发明的目的组合物6〇 [0049] Take 50g above-prepared composition was placed in a beaker 3, an amount of an aqueous solution taken 1.7gPd 3000yg / g and a content 0.6gRh 4000yg / g was placed in beaker 4, 4 in a beaker and then added 22.7g of distilled water stir the mixture was stirred 4 in the case where the beaker was slowly added in 3 beaker, stirred solution was added after a further 30 minutes, allowed to stand for 10 hours to impregnate the above-described baking in an oven at 120 ° C for 6 hours, and then in a muffle oven baked for 5 hours at 620 ° C, to obtain the composition object of the present invention 6〇

[0058]表1为组合物性能测试过程中所用FCC平衡剂的性质。 [0058] Table 1 shows the properties of the composition in the nature of the test agent with the FCC equilibrium.表2为本发明组合物的NO和CO脱除性能测试评价结果。 Table 2 composition of the present invention, CO and NO removal performance test results of the evaluation.

[0065] 以上所述的实施例仅用于说明本发明的技术思想及特点，其目的在于使本领域内的技术人员能够理解本发明的内容并据以实施，不能仅以本实施例来限定本发明的专利范围，即凡本发明所揭示的精神所作的同等变化或修饰，仍落在本发明的专利范围内。 Example [0065] The above-described technical idea is for illustration only and features of the invention, its object is to enable a person skilled in the art to understand the present invention and accordingly embodiment, not only the present embodiment is defined equivalent variations or modifications patentable scope of the invention, i.e., where the spirit of the disclosed invention is made present, still fall within the scope of the present invention.

4. 如权利要求1-3任一项所述的方法制备的用于降低催化裂化再生烟气NOx排放并具有C0助燃功能的组合物。 4. A method according to any one of claims 1-3 in the preparation of FCC regenerator flue gas for reducing NOx emissions and combustion C0 having a functional composition.

5. 根据权利要求4所述的用于降低催化裂化再生烟气NOx排放并具有C0助燃功能的组合物，其特征在于，所述组合物的比表面积不小于50m 2/g。 According to claim FCC regenerator flue gas for reducing NOx emissions and combustion C0 having a functional composition of claim 4, wherein a specific surface area of ​​the composition is not less than 50m 2 / g.